DE2628195B1 - PROCESS FOR THE PRODUCTION OF AMIDOSULPHIC ACIDS - Google Patents

Description

R ¹ -N = C

R ²

R ³

(II)

where R ² and R ³ each denote an aliphatic, cycloaliphatic hydrocarbon radical or the furyl radical, R ^{2 can} also stand for a hydrogen atom, reacts with sulfur trioxide and treats the addition compound formed or the reaction mixture containing the addition compound formed with water.

It is from Houben-Weyl, Methods of Organic Chemistry, Volume 11/2, pages 654 and 655, known that Ν, Ν'-dialkylureas by action first sulfated by oleum and then split to amidosulfonic acids. A work in the Journal of the American Chemical Society, Vol. 75, pp. 1409-1412 (1953) also shows that of Houben-Weyl described reaction with oleum without further aftertreatment; it is explicitly based on the difficulty pointed out to achieve an optimum of yield in the reaction and in particular the formation of Suppress or reduce alkylammonium sulfate. The time of adding the starting materials and the Temperature control of the reaction play a significant role. When working up, the end product must washed several times with ether, but still contains sulfate and despite these cleaning operations can only be purified by dissolving in methanol and precipitating by adding larger amounts of ether. US Pat. No. 3,555,081 describes the synthesis of N-cyclohexylamidosulfonic acid and also shows that the use of sulfuric acid leads to contaminated end products According to their teaching (column 3, lines 45 to 54) it is crucial that no sulfuric acid is present in the reaction mixture. With two-stage Sulfuric acid may only work together with sulfur trioxide in the form of oleum in the second Reaction step can be used.

It is known from German Offenlegungsschrift 21 64 197 that isocyanates can be mixed with sulfuric acid at elevated temperature in organic solvents to form sulfamic acids

With regard to the toxic and, in some cases, difficult to access starting materials, the process is the difficult conduct of the reaction and the moderate yield unsatisfactory.

The manufacturing process defined in the claim has now been found.

The claimed implementation can for the case of the use of ethylidene isopropylamine by the the following formulas can be reproduced:

_{/ C} H ₃

+ SO ₃
H
CH ₃

HCN = C
CH ₃
CH ₃

HCH ₃ C

-N = C

(III)

H ₂ O

CH ₃ H
HCN-SO ₃ H + CH ₃ -CHO

CH ₃

In comparison to the known process, the process according to the invention surprisingly provides amidosulfonic acids in good yield and purity in a simpler and more economical way, starting from more easily accessible starting materials. Since the ketones and aldehydes recovered in the reaction can be converted back into the Schiff bases with the amines, the process according to the invention provides the possibility of preparing amidosulfonic acids _{from amines and SO 3 via Schiff bases.} In comparison to the processes with isocyanates as starting materials, it is also more environmentally friendly and more reliable.

Preferred starting materials II and correspondingly preferred end products I are those in whose formulas R ¹ denotes an alkyl radical having 1 to 20, preferably 1 to 10 carbon atoms or a cycloalkyl radical having 4 to 8 carbon atoms, R ² and R ^{3 are} identical or different and each have one Denote alkyl radical with 1 to 20, preferably 1 to 10 carbon atoms or a cycloalkyl radical with 4 to 8 carbon atoms or a furyl radical, R ^{2 can} also stand for a hydrogen atom. The aforementioned radicals can also be replaced by groups which are inert under the reaction conditions,

z. B. alkyl groups having 1 to 4 carbon atoms, may be substituted.

For example, the following Schiff bases are suitable as starting materials II:

Methyl, ethyl, n-propyl, isopropyl, n-butyl,
Isobutyl, sec-butyl, tert-butyl, pentyl,
Pentyl- (2) -, pentyl- (3) -, n-hexyl-, n-heptyl-,

n-octyl, n-nonyl, n-decyl, 2-ethylhexyl,
^, ö-trimethyl-n-heptyl - ^ - ethylpentyl-,
3-ethylpentyl-, 2,3-dimethyl-n-butyl-,
2,2-dimethyl-n-butyl-, 2-methylpentyI-,
3-methylpentyl, cyclobutyl, cyclopentyl,

Cyclohexyl-, cycloheptyl-, cyclooctyl-imine of
Acetaldehyde, propionaldehyde, n-butyraldehyde,
iso-butyraldehyde, 2-methyl-butyraldehyde,
2-ethyl-caproaldehyde, n-valeraldehyde,

ORIGINAL INSPECTED

Isovaleraldehyde ^^ - Dimethyl-propionaldehyde, n-caproaldehyde, isocaproaldehyde, 2-methyl-valeraldehyde, 3-methyl-valeraldehyde, 2-ethyl-butyraldehyde, 2,2-dimethylbutyraldehyde, 2,3-dimethylbutyraldehyde,

3,3-dimethylbutyraIdehyde, önanthaldehyde, 2-methyl-capΓonaldehyde, 3-methyl-capΓonaIdehyde, ^ Methyl-caproaldehyde, S-methyl-caproaldehyde,

a-ethylvaleraldehyde, a-dimethylvaleraldehyde, 2,3-Dimethylvalaldehyde, 4-ethylvalaldehyde, 4,4-dimethyl aldehyde,

3,4-dimethyl aldehyde,

2,4-dimethylvaleraldehyde,

2-EthyI-2-methyl-butyraldehyde, 2-EthyI-3-methyl-butyraldehyde, acetone, Methyl ethyl ketone, methyl n-propyl ketone, Methyl isopropyl ketone, methyl n-butyl ketone, Methyl isobutyl ketone, methyl selc-butyl ketone, Methyl tert-butyl ketone, methyl n-pentyl ketone, methyl pentyl (2) ketone, methyl pentyl (3) ketone, Methyl isoamyl ketone,

Methyl (2-methyl) butyl ketone,

Methylol methyl) butyl ketone,

Methyl (2-ethyl) butyl ketone,

Methyl (3-ethyl) butylketone,

Methyl (2,2-dimethyl) butyl ketone, methyl (2,3-dimethyl) butyl ketone, Methyl (3,3-diniethyl) butyl ketone;

correspondingly unsymmetrical ketones that replace the methyl group with the

Ethyl, n-pentyl, isopropyl, η-butyl, isobutyl, selc-butyl-, terL-butyl-, n-pentyl-, pentyl- (2) -, Pentyl- (3) -, isoamyl-, (2-methyl) -butyl-,

(1 -Methyl) -butyl-, (2-ethyl) -butyh (3-ethyl) -butyl-, (2 ^ -dimethyl) -butyl-, (2 _> 3-dimethyl) -butyl-, (3.3 -Dimethyl) -butyl group; Diethyl ketone, di-n-propyl ketone, di-iso-propyl ketone, di-n-butyl ketone, di-iso-butyl ketone, di-sec-butyl ketone, di-tert-butyl ketone, di-n-pentyl ketone, dipentyl (2) -ketone, dipentyl- (3) -ketone, diisoamylketone, di- (2-methyl) -butylketone, di- (1-methyl) -butylketone, di- (2-ethyl) -butylketone, di- (3-ethyl) -butyIketon,

Di (2,2-dimethyl) butyl ketone,

Di (2,3-dimethyl) butyl ketone,

Di (33-dimethyl) butyl ketone, cyclohexyl, Cyclopentyl aldehyde, dicyclopentyl ketone,

Dicyciohexyl ketone; Furfural;

The Schiff bases listed in the examples are preferred.

The reaction is expediently in the first step with 0.8 to 1.5, preferably 0.95 to 1.1 mol Sulfur trioxide and in the second step with 1 to 10, preferably 1 to 2 mol of water per mol of starting material II carried out. Sulfur trioxide can be used in solid form or conveniently in liquid form or as a gas Apply; 100 percent sulfur trioxide is advantageous, if necessary it can also be diluted with inert gas such as carbon dioxide. But you can also use substances under the reaction conditions Release sulfur trioxide, use, for example addition compounds of sulfur trioxide, e.g. B. with ethers such as tetrahydrofuran, di - (/? - chloroethyI) ether, 1,4-dioxane; Ν, Ν-disubstituted carboxamides such as Ν, Ν-dimethylformamide; with tertiary Amines, e.g. B.

Pyridine, triethylamine, trimethylamine, tributylamine, quinoline, quinaldine, dimethylaniline, triphenylamine, N-methylmorpholine, N-ethylmorpholine,
N-methylpiperidine, N-ethylimidazole,
N-methylethyleneimine,
N-ethylpentamethyleneimine;

or addition compounds of chlorosulfonic acid with the aforementioned amines, in particular pyridine; or corresponding mixtures. Substances that contain sulfuric acid, e.g. B. Oleum, do not come in place of Sulfur trioxide into consideration. With regard to the definition of 100 percent sulfur trioxide, see Ullmanns Encyclopedia of Industrial Chemistry, Volume 15, pages 465 to 467 and for the preparation of addition compounds see Houben - Weyl, (loccit) B3nd VI / 2, pages 455 to 457 and Volume IX, Pages 503 to 508.

The reaction in two steps in 3llgemeinen at a Temperstur from - 30 ⁰ C to 150 ⁰ C, in the first step suitably from -30 to + 100, preferably from -20 to +30 ⁰ C, expediently in the second step from -20 to +150 ⁰ C, preferably ^{-10 to +100 0} C, carried out without pressure or under pressure, continuously or batchwise. Organic solvents which are inert under the reaction conditions are advantageously used in both steps, the total amount of organic solvent advantageously already being added to the first reaction step. As a solvent, for. B. in question:

Halogenated hydrocarbons,
especially chlorinated hydrocarbons,
z. B. tetrachlorethylene, amyl chloride,

Methylene chloride, dichlorobutane, isopropyl bromide,
n-propyl bromide, butyl bromide, chloroform,
Chloronaphthalene, dichloronaphthalene,
Carbon tetrachloride, tetrachloroethane,
Trichloroethane, trichlorethylene, pentachloroethane,
Trichlorofluoromethane, cis-dichloroethylene, o-, m-,
p-difluorobenzene, 1,2-dichloroethane,
1,1 -dichloroethane, n-propyl chloride,
1,2-cis-dichloroethylene, n-butyl chloride, 2-, 3- and
isobutyl chloride, chlorobenzene, fluorobenzene,
Bromobenzene, iodobenzene, o-, p- and
m-dichlorobenzoI, o-, p-, m-dibromobenzoI, o-, m-,
p-chlorotoluene, 1,2,4-trichlorobenzene,
1,10-dibromodecane, 1,4-dibromobutane;

aliphatic or cycloaliphatic hydrocarbons, e.g. B. heptane, pinane, nonane, gasoline fractions within the boiling point range of 70 to 190 ⁰ C, cyclohexane, methylcyclohexane, petroleum ether, decalin, pentane, hexane, ligroin, 2,2,4-trimethylpentane, 2,2,3-trimethylpentane, 2 , 3,3-trimethylpentane, octane; and corresponding mixtures. The solvent is expediently used in an amount of 100 to 10,000 percent by weight, preferably 100 to 1000 percent by weight, based on starting material I.

You can separate the addition compound from the reaction mixture after the first step, for. B.

by filtration or removal of the solvent, and then the addition compound again to the second Feed step. In general, however, for economic and operational reasons, the

Carry out implementation of both steps in succession without disconnecting the addition compound and thus treat the reaction mixture of the first step directly with water.

The reaction can be carried out as follows: A mixture of starting material II, if appropriate organic solvent, and sulfur trioxide is for 0.2 to 3 hours at the reaction temperature held. Advantageously, sulfur trioxide is first placed in a solvent and the starting material II added with thorough mixing. Then water is added and the mixture in the second Reaction step held at the reaction temperature for 0.5 to 2 hours. Now the Reaction mixture of the end product in the usual way, for. B. by filtration, separated.

The compounds which can be prepared by the process of the invention are sweeteners, in particular cyclohexylamido sulfonic acid or their calcium, sodium and potassium salts, and valuable starting materials for the Manufacture of sweeteners, colors and pesticides. For example, through Chlorination, e.g. B. with thionyl chloride, the corresponding sulfonic acid chlorides, e.g. B. Isopropylaminosulfonyl chloride, getting produced; they can be converted into anthranilic acid or its salts the o-sulfamidobenzoic acids described in the German Offenlegungsschrift 21 04 682 produce. By cyclizing these substances, e.g. B. after that described in German Offenlegungsschrift 21 05 687 Process, one arrives at the 2, l, 3-Benzothiadiazin-4-one-2,2-dioxides, their use for pesticides and pharmaceuticals in the same patent is described. With regard to the use, reference is made to the aforementioned publications and to DAS 11 20 456, DP 12 42 627 and DOS 15 42 836 referenced.

The parts listed in the following examples are parts by weight.

example 1

80 parts of SO ₃ are dissolved in 120 parts of dichloroethane and cooled to -20 ⁰ C. 113 parts of isobutylidene isopropylamine in 100 parts of dichloroethane are added over the course of 20 minutes; the temperature rises slowly to 0 ^° C. The mixture is stirred an hour and then for 10 minutes at 0 ⁰ C. 18 parts of water. After stirring for one hour the mixture is filtered off and, after drying, 136 parts (98.5% of theory) Isopropylamidosulfonsäure mp. 171 ⁰ C. Isobutyraldehyde was separated from the filtrate by distillation and transferred to fresh isopropylamine in the Schiff base.

Example 2

80 parts of SO ₃ in 100 parts of dichloroethane at - 10 ⁰ C presented. 99 parts of isopropylideneisopropylamine in 100 parts of dichloroethane are added at this temperature over a period of 30 minutes. 18 parts of water are then added at 10 ^{° C. over the course of 10 minutes.} If one now draws the end product formed from 131 parts of and, after drying (95% of theory) Isopropylamidosulfonsäure mp. 170 ⁰ C.

Example 3

To 80 parts of SO ₃ in 100 parts of chloroform is added 101 parts Pivalinaldehydisopropylamin for 30 minutes at 0 ⁰ C in 100 parts of chloroform. Analogously to Example 1, 120 parts (87% of theory) of isopropylamidosulfonic acid are obtained.

Example 4

To 19.25 parts of SO ₃ in 50 parts of dichloroethane are added 20.4 parts Äthylidenisopropylamin for 15 minutes at -10 ^0C. After stirring for one hour, the mixture is treated at 5 ° C. with 4.5 parts of water. After filtration and drying, 28.3 parts (85.5% of theory) of isopropylamidosulfonic acid with a melting point of 170 ^° C. are obtained.

Example 5

45.4 parts of isobutylidenecyclohexylamine are added at -10 ° C. to 19.25 parts of SO ₃ in 100 parts of dichloroethane over the course of 30 minutes. Subsequently, the mixture is stirred for one hour at 0 ⁰ C and then treated with 4.5 parts of water for 5 minutes at 0 ⁰ C. The suspension formed is by l, filtered 5 hours stirring time and the mother liquor under 40 mbar evaporated The residue is combined with the filtered material and dried. 42.0 parts of cyclohexylamidosulfonic acid (97.5% of theory) with a melting point of 169 ° C. are obtained.

Example 6

To 19.25 parts of SO ₃ in 100 parts of dichloroethane are added 32.8 parts Furfurylidenisopropylamin for 15 minutes at -10 ^0C. The reaction solution turns at the beginning of adding red-violet and brightens the late addition "again. The mixture is stirred for 1.5 more hours at -10 ⁰ C. Then there are added at this temperature with 4.5 parts water The The yellow precipitate which forms after 30 minutes is filtered off and dried, giving 23.6 parts (78% of theory) of isopropylamido sulfonic acid with a melting point of 167 ° C.

Example 7

To 21.5 parts of SO ₃ in 150 parts of 1,2-dichloroethane, 64.5 parts Isobutylidendodecylamin is added for 15 minutes in 100 parts of dichloroethane at -10 ⁰ C. The solution was heated for one hour at 0 ⁰ C, and added quickly 4 , Add 9 parts of water. After a further 15 minutes, a finely crystalline precipitate forms. Filtration and drying give 65 parts of dodecylamido sulfonic acid with a melting point of 160 ° C. (with decomposition).

Example 8

a) 31 parts of SO ₃ are presented in 70 parts of CCl ₄ . 43.8 parts Isobutylidenisopropylamin to 100 parts in CCl ₄ 10 ⁰ C within 40 minutes - now you are at. After the addition is complete, the mixture is filtered off and dried. 74.5 parts of addition compound of the formula are obtained as filter material

CH ₃ H

I e I

HC-N = C-

I I

CH ₃ SCf

CH,

CH ₃

(IV)

of melting point 72 ° C. (with decomposition).

b) 50 parts of the aforementioned addition compound are dissolved in 100 parts of chloroform at - slurried 10 ⁰ C and 4.7 parts of water were added. The mixture is stirred at - 10 ⁰ C 15 minutes, filtered and dried to give 35 parts Isopropylamidosulfonsäure of mp 171 ^0C.

Claims (1)

Claim: Process for the preparation of sulfamic acids of the formula in which R ¹ denotes an aliphatic or cycloaliphatic hydrocarbon radical, characterized in that Schiff bases of the formula